Epoxy-organo silicon compounds as hair treating agents



United States Patent 7 Claims. (a. 167-87) 3,248,296 Patented Apr. 26, 1966 ether, silicon-linked substances, of the following formula can be obtained, for example, wherein:

The invention relates to a treatment of human hair, the purpose of which is that the hair, particularly after it has been curled or waved with known agents, will keep its shape for a long time even under the influence of moisture.

For this treatment according to the invention there is put onto the hair an epoxy organo siloxane of the general formula wherein n is a numerical value greater than 1.9 and has a maximum of 3. Of the individual substituents R at least one is an epoxidised, CSi linked organic radical, i.e., containing the epoxide group -CH-CH the others being methyl radicals which may be replaced to a small extent by hydrogen or CSilinked optionally also esterified polyether radicals. The epoxidised organic radicals can also contain the epoxide group several times so that up to 7 epoxide groups can be connected through organic radicals withone silicon atom. For every 100 silicon atoms the siloxane employed should contain at least one epoxide group, and in general at the most 250.

The epoxidised organo siloxanes can be produced in various ways not claimed herewith. For example, alkenyl silicon compounds can be oxidised with peracetic acid to epoxy alkyl silicon compounds, or partially substituted siloxanes can be added with their --HSigroups to the double bonds of olefinic epoxides, e.g., epoxybutene or allyl glycidyl ether, to obtain for example silicon-linked Furthermore amino alkyl or polyamino alkyl or -arylsiloxanes can be reacted with polyepoxides in such proportions that part of the epoxide groups remain unchanged. Thus by using butane diol-(l,3)-diglycidyl ether or 4,4 dioxydiphenyldimethylmethane diglycidyl The CAP-linked polyether radicals which the siloxanes to be used according to the invention can contain, besides the epoxidised organic radicals and the methyl 0 radicals, correspond for example to the formulae In this formula x is a whole number from 1 to 3, m is a whole number from 1 to 20, each individual group OR"- is ethylene oxide or propylene oxide, each individual radical R is hydrogen, lower alkyl or carboxyl.

These optionally esterified polyether radicals increase the solubility in water and alcohols. They can be introduced into siloxanes rich in epoxide groups, for example, by causing polyalkylene glycols to react with some of the epoxide groups or by adding siloxanes with HSigroups on to olefinic polyethers in such a way that some of these groups at first remain over which are then added onto olefinic epoxide, groups, or as described in detail in copending application Serial No. 205,558, filed June 27, 1962, in the name of Walter Simmler and Hans-Werner Kauczor, which application has been assigned to the assignee of this case by reacting polyalkylene glycols with bromomethyl siloxanes in such a way that part of the bromo methyl radicals are initially retained, and these are then reacted with amines or polyamines, and the amino groups, as already described, are finally caused to react with polyepoxides. The forementioned application is now US. 3,174,987 patented on March 23, 1965.

The epoxy organo siloxane can be employed according to the invention :as the substance itself or as a solution, for example in water, ethanol, or methylene chloride. The effect of the hair treatment can be demonstrated as follows:

A curl is formed in known manner by rolling a lock of human hair on a commercial curler, impregnating it with an 'aqueous solution of 6% by weight of thioglycollic acid and 4% by weight of cthanolamine, heating for half available under the registered trademark Lekutherm an hour at 50 C., then thoroughly rinsing with water, X-20 as an epoxide resin precursor, is added to a soludipping for 5 minutes into an aqueous solution of 3% tion of 10.6 grams of an aminoalkyl siloxane of the by weight of hydrogen peroxide, rinsing again and drying formula at 60 C. The lock of hair taken off the curler and now 5 spiral shaped, is thoroughly moistened with one of the NHZ i treating agents specified 1n the followlng examples, the

curl is dried for half an hour at 60 C. and subjected to the following test; in 30 grams of methylene chloride so that the number of The lock of hair is moistened with water, a 5 gram- 10 epoxide groups is double the number of nitrogen-linked weight is fastened to one end and at the other end it is hydrogen atoms of the siloxane used. The mixture is fixed to hang freely in a heated cabinet, and the hair thus stirred for one hour at room temperature and then diluted loaded is again dried at 60 C. If the siloxane applicawith 2,000 grams of methylene chloride. 7 tion is omitted, the dried and unloaded lock of hair has A lock of hair is treated with the solution obtained, in lost its spiral form after this treatment and is quite straight. the manner described, with the result that the straighten- The hair treated according to the invention, on the other ing experiment gives no noticeable alterations to the hand, is covered with an elastic film which protects it shape of the hair. I from the penetration of water without making the hairs stick to each other.

The following-examples are given for the purpose of illustrating the invention.

Example 4 The same results as in Example 3 are obtained by using the epoxy organo siloxane obtained in the following Way:

19 grams of a diepoxide of the formula c HzC H-o HTOC 112-0 112-0 112-0 HOCHzCg/C H An ethyl alcoholic solution of 1% by Weight of an O 9 H3 0 epoxy organo siloxane is used which is produced from is added to a solution of 19 grams of an aminoalkyl silox- 2985 grams of a siloxane of the composition ane of the formula Example 1 L Jr L Jo

in 45 grams of methylene chloride, and the mixture is stirred for one hour at room temperature. It is then diluted with 3,500 grams of methylene chloride and this solution is applied as described in Example 3.

2(CH3)3S10 1s (CH3) SiO -18CH S|iO 2 H and 2690 grams of allylglycidyl ether in the presence of 5 grams of a catalyst of aluminium oxide (according to Brockmann) with 2% by weight of platinum deposited thereon, and exhibits a content of 16.3% by weight of Example 5 The same stability of shape in the straightening experithe group ment which is achieved in Examples 3 and 4 is attained with a product produced as follows:

An aminoalkyl siloxane ether of the formula and 0.12% by weight of residual silicon-linked hydrogen. OSi(CH -O Si(CH CH L Q R A lock of hair treated with this solution in the manner L J L .1 described above has a silky sheen without appearing 1 greasy. Under the straightening treatment described it CHPSFOIslam)r0131(CH@)TCH1tNH-CH=-CHTNH1 substantially retains its shape.

' Example 2 O a)2- a)r- H0R OC4 a L J L J 100 grams of the epoxy organo polysiloxane according to Example 1 is modified by heating it to 150 C. with 38 grams of a polyethylene glycol containing 8.7% by Weight 0f P and W gram of anhYdTQuS of this compound in 70 grams of methylene chloride, 6.5 Sodlum hydroxldfi- PP Y half eP0Xlde grams are added of the same diepoxide as in Example 4, groups Introduced are thereby Fthel'lfied W1th the P 3- and the mixture is stirred for one hour at room temperaethylene y 9 The Product 15 soluble If a ture. The methylene chloride is then blown off at 30 lock of halr 1s treated 1 1 the ma r q vfllth an C. with nitrogen and the remaining oil is dissolved in aqueous Solutlon of 1% y Weight of thls Polyslloxane 5,200 grams of aqueous ethyl alcohol containing 70% product, this lock of hair substantially retains its shape by weight f ethanoL i Solution is applied as 1 also in the straightening experiment. ib d i th foregoing examples,

We claim: 1. A composition for increasing hairs stability of shape against the influence of moisture consisting essentially of a solution of approximately 1% by weight of an organopolysiloxane in a diluent selected from the group consisting of Water, ethanol, aqueous ethanol, and methylene chloride, said organo-polysiloxane having the formula is used wherein -EOR"3- represents a polyalkylene oxide chain composed of equal parts by weight of ethylene oxide and propylene oxide. To a solution of 46 grams Example 3 An epoxy organo siloxane is used which is obtained in the following way:

12.6, grams of a commercial condensate of an ether of the formula wherein n has a value of from 1.9 to and including 3, each R is a member selected from the group consisting of CfiSi bonded epoxy-organo selected from the group 2. A method of treating hair for increasing the hairs stability of shape against the influence of moisture, which comprises applying to the hair with the hair positioned consisting of in the arrangement in which it is desired to be stabilized H OH2, a composition consisting essentially of a solution of ap- O O proximately 1% by Weight of an organo-polysiloxane in a diluent selected from the group consisting of water, CH2 CHQCHZ OCHT'CE7CH ethanol, aqueous ethanol, and methylene chloride, said 0 organo-polysiloxane having the formula o m m-cm-o n-o rn0-R'-oo Hz-CHCH2)2 /m' (5H T wherein n has a value of from 1.9 to and including 3, and each R is a member selected from the group consisting cH, 1|\r-o H2C Hz N(CH -(l3 11-0 Hr-OR-OC H2CHC H2);

our OH o noon (IJHz 0 Bl I o wherein m is a whole number from 1 to 5, inclusive, and

of CSibonded epoXy-organo selected from the group R is a member selected from the group consisting of consisting of OH; and

methyl, hydrogen, and C-Si-bonded polyether radicals wherein m is a whole number from 1 to 5, inclusive, having the formulas and R is a member selected from the group consisting of CH2-CH2-?H n! wherein x is a whole number from 1 to 3, inclusive, m is H f l a whole number from 1 to 20, inclusive, R" is alkylene 7 having 2 to 3 carbon atoms, R' is a member selected from the group consisting of hydrogen, alkyl having from (OxH2x)CHCH2 0 RT0'R 1 to 4 carbon atoms, and carboxyl, wherein said epoxy- 70 organo group members have from 1 to 7 epoxide groups, the proportion of said epoxy organo-group members being such that the number of the epoxide groups to the num- (CXH2 L L ber of silicon atoms contained in said organo-polysiloxane j is in the ratio of 1:100 to 25:10. 7

having the formulas wherein x is a whole number from 1 to 3, inclusive, m is by weight of an organo polysiloxane which is the reaction a whole number from 1 to 20, inclusive, R" is alkylene product of having 2 to 3 carbon atoms, R'" is a member selected from the group consisting of hydrogen, alkyl having from CH:

1 to 4 carbon atoms, and carboxyl, wherein said epox 5 l organo group members have from 1 to 7 epoxide group s, g 7 7 the proportion of said epoxy organo-group members being 0 3 0 such that the number of the epoxide groups to the number of silicon atoms contained in said organo-polysiloxane and is in the ratio of 100 to :10, and then drying the'hair 6. A composition for increasing hairs stability of shape with the compositlon thereon. v against the influence of moisture consisting essentially of 3 A composition for increasing halrs stability of shape a methylene chloride solution of approximately 1% by against the influence of moisture consisting essentially of weight of an organo polysiloxane which is the reaction an ethanolic solution of 1% by weight 'of an epoxy product of organo-siloxane which is the reaction product of 2 H and OESi(CH;)zO-3Si(CHQz-CHzNHCH2CHz-NHCHz-CHr-NH:

5 ES a)r- :l- S z)2-CH:NHCHzCHaNH-CH2CH2NH2 fl O-E-Si(CH3)aO3-Si(CHa)2-CHg-NHCHz-CHzNHCHr-CHzNHa and allylglycidyl ether having a content of 7. A composition for increasing hairs stability of shape against the influence of moisture consisting essentially of 0 an ethanolic solution of approximately 1% by weight of an organo polysiloxane which is the reaction product of groups of 16.3% by weight and 0.12% by welght of residual silicon-linked hydrogen.

4. A composition for increasing hairs stability of shape 40 0 CH3 I 0 against the influence of moisture consisting essentially and L Jr 011a-s1o|- :s1 oHa)ro}si(oH=)=cHrNH0HoHhNH-cHz-CHz-NH:

5 K s)z0 I-S (C s)2CHz-NH-CHz-OHz-NH-CHzCHzNH2 of an aqueous solution of 1% by weight of an organo References Cited by the Examiner polysiloxane is the reaction product of 2(CH SiO .18(CH3)zSi0.18CH SiO 2,750,947 6/1956 Gant 167-87.1 XR 5 2,970,150 1/1961 Snyder 260348 3,061,519 10/1962 Rosekrans 16787 and a polyethylene glycol containing 8.7% by weight of FOREIGN PATENTS OH groups so that half of the epoxide groups introduced 5 G are etherified with the polyethylene glycol. 0 1,061,321 7/19 9 Mummy- 5. A composition for increasing hairs stability of shape against the influence of moisture consisting essentially JULIAN LEVITT"Pmar-y Examiner of a methylene chloride solution of approximately 1% FRANK CACCIAPAGLIA, JR., Examiner. 

2. A METHOD OF TREATING HAIR FOR INCREASING THE HAIR''S STABILITY OF SHAPE AGAINST THE INFLUENCE OF MOISTURE, WHICH COMPRISES APPLYING TO THE HAIR WITH THE HAIR POSITIONED IN THE ARRANGEMENT IN WHICH IT IS DESIRED TO BE STABILIZED A COMPOSITION CONSISTING ESSENTIALLY OF A SOLUTION OF APPROXIMATELY 1% BY WEIGHT OF AN ORGANO-POLYSILOXANE IN A DILUENT SELECTED FROM THE GROUP CONSISTING OF WATER, ETHANOL, AQUEOUS ETHANOL, AND METHYLENE CHLORIDE, SAID ORGAN-POLYSILOXANE HAVING THE FORMULA 